Water-soluble Quinacridones

ABSTRACT

The use of water-soluble quinacridones of the formula I ##STR1## where M.sup.⊕  is a lithium, sodium, potassium or ammonium cation, 
     R 1 , R 2 , R 3  and R 4  independently are hydrogen, C 1  -C 8  -alkyl, C 1  -C 8  -alkoxy, carboxyl, C 1  -C 4  -alkoxycarbonyl, sulfamoyl, mono- or di-(C 1  -C 4 )-alkylsulfamoyl, carbamoyl, mono- or di-(C 1  -C 4 )-alkylcarbamoyl, unsubstituted or substituted mono- or diphenylsulfamoyl, unsubstituted or substituted mono- or diphenylcarbamoyl, halogen, nitro or cyano, 
     n is 0, 1 or 2 and 
     m is 0, 1 or 2 and the sum n+m is at least 1, 
     for dyeing and printing natural and synthetic fiber material.

The present invention provides for the use of water-solublequinacridones of the formula I ##STR2## where M.sup.⊕ is a lithium,sodium, potassium or ammonium cation,

R¹, R², R³ and R⁴ independently are hydrogen, C₁ -C₈ -alkyl, C₁ -C₈-alkoxy, carboxyl, C₁ -C₄ -alkoxycarbonyl, sulfamoyl, mono- or di-(C₁-C₄)-alkylsulfamoyl, carbamoyl, mono- or di-(C₁ -C₄)-alkylcarbamoyl,unsubstituted or substituted mono- or diphenylsulfamoyl, unsubstitutedor substituted mono- or diphenylcarbamoyl, halogen, nitro or cyano,

n is 0, 1 or 2 and

m is 0, 1 or 2 and the sum n+m is at least 1,

for dyeing and printing natural and synthetic fiber material, andprovides recording liquids comprising them. The invention also relatesto soluble quinacridones with an ammonium cation.

JP-A 5 004 019 and JP-A 46 010 069 disclose pigment mixtures containingsalts of primary, secondary or tertiary amines of sulfonatedquinacridones.

Furthermore, U.S. Pat. No. 3,386,843 describes the sodium salt ofsulfonated quinacridone as a precursor in the preparation of aluminumquinacridonesulfonic acids.

These salts are employed as crystallization disruptors for quinacridonepigments in order to improve their dispersing properties.

JP-A 05 222 328 discloses quinacridones having2-carboxybenzoylaminomethylene substituents in mixtures of colorants forinkjet printing.

The use of quinacridone pigments in graphic inks and printing inks isgenerally known but in general is hampered by the problem of unstablecolorant mixtures. This can lead to the deposition of solid substancesand thus to the blockage of nozzles, which often totally rules out theuse of quinacridone pigments in recording liquids such as inks.

If soluble colorants, ie. dyes, instead are used in inks, then the wetfastness of the resultant prints is usually inadequate.

It is an object of the present invention, therefore, to provide inkjetcoloring techniques with colorants which solve the problems of the priorart.

We have found that this object is achieved by the use of thewater-soluble quinacridones defined at the outset for dyeing andprinting natural and synthetic fiber material, especially for the pulpdyeing of paper and for inkjet printing processes.

The quinacridones have up to four, preferably three, two or one sulfogroup in anion form. Particular preference is given to quinacridoneshaving two sulfo groups.

Suitable cations M.sup.⊕ are lithium, sodium, potassium or, preferably,ammonium ions. For the purposes of the invention, ammonium ions can besubstituted or unsubstituted ammonium cations. The former includemonoalkyl-, dialkyl-, trialkyl-, tetraalkyl- or benzyltrialkylammoniumcations or those cations derived from nitrogen-containing 5- or6-membered saturated heterocycles. Alkyl is generally straight-chain orbranched C₁ -C₂₀ -alkyl which can be substituted by 1 or 2 hydroxylsand/or interrupted by 1 to 4 oxygens in ether function. Where theammonium ions have one or more alkyls, the latter can be identical ordifferent.

Particular mention may be made of mono-C₁ -C₆ -alkylammonium, di-(C₁ -C₆-alkyl)ammonium, tri-(C₁ -C₆ -alkyl)ammonium, tetra-(C₁ -C₆-alkyl)ammonium, benzyltri-(C₁ -C₆ -alkyl)ammonium, pyrrolidinium,piperidinium, morpholinium, piperazinium or N-(C₁ -C₄-alkyl)piperazinium ions.

Suitable amines from which the ammonium ions are derived are, forexample:

monoalkylamines, such as methylamine, ethylamine, propylamine,isopropylamine, butylamine, sec-butylamine, isobutylamine,1,2-dimethylpropylamine or 2-ethylhexylamine,

dialkylamines, such as dimethylamine, diethylamine, dipropylamine,diisopropylamine, dibutylamine, diisobutylamine, di-sec-butylamine,bis-(2-ethylhexyl)amine, N-methyl-n-butylamine or N-ethyl-n-butylamine,

alkoxyalkylamines, such as 2-methoxyethylamine, bis-2-methoxyethylamine,3-methoxypropylamine, 3-ethoxypropylamine or3-(2-ethylhexoxy)propylamine,

trialkylamines, such as trimethylamine, triethylamine,tri-n-propylamine, tributylamine, N,N-dimethylethylamine,N,N-dimethylisopropylamine, N,N-dimethylbenzylamine and

hydroxyamines, such as mono- or diethanolamine, mono- ordipropanolamine, mono- or diisopropanolamine, N-mono- or N,N-di-(C₁ -C₄-alkyl)ethanolamines, -propanolamines or -isopropanolamines, such asN-mono- or N,N-dimethylethanolamine, -propanolamine or-isopropanolamine, N-mono- or N,N-diethylethanolamine, -propanolamine or-isopropanolamine, N-mono- or N,N-dipropylethanolamine, -propanolamineor -isopropanolamine, N-mono- or N,N-diisopropylethanolamine,-propanolamine or -isopropanolamine or N-mono- orN,N-dibutylethanolamine, -propanolamine or -isopropanolamine, N-(C₁ -C₄-alkyl)diethanolamines, -dipropanolamines or -diisopropanolamines, suchas N-methyldiethanolamine, -dipropanolamine or -diisopropanolamine,N-ethyldiethanolamine, -dipropanolamine or -diisopropanolamine,N-propyldiethanolamine, -dipropanolamine or -diisopropanolamine,N-isopropyldiethanolamine, -dipropanolamine or -diisopropanolamine orN-butyldiethanolamine, -dipropanolamine or -diisopropanolamine,triethanolamine, tripropanolamine, triisopropanolamine,N-(2-hydroxyethyl)pyrrolidine, N-(2- or 3-hydroxypropyl)pyrrolidine,N-(2-hydroxyethyl)piperidine, N-(2- or 3-hydroxypropyl)piperidine,N-(2-hydroxyethyl)morpholine, N-(2- or 3-hydroxypropyl)morpholine,N-(2-hydroxyethyl)piperazine, N-(2- or 3-hydroxypropyl)piperazine orN,N-dimethyl- or N,N-diethyl-N-(5-hydroxy-3-oxapentyl)amine.

Examples of R¹, R², R³ and R⁴ are methyl, ethyl, propyl, isopropyl,butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl,tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl,2-ethylhexyl, isooctyl (the above designation isooctyl is a trivial nameand derives from the alcohols obtained by oxo synthesis--cf. in thisrespect Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition,Vol. A 1, pages 290 to 293, and also Vol. A 10, pages 284 and 285),methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy,tert-butoxy, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl,sec-butoxycarbonyl, tert-butoxycarbonyl, mono- or dimethylsulfamoyl,mono- or diethylsulfamoyl, mono- or dipropylsulfamoyl, mono- ordibutylsulfamoyl, mono- or dimethylcarbamoyl, mono- or diethylcarbamoyl,mono- or dipropylcarbamoyl, mono- or dibutylcarbamoyl, fluorine,chlorine and bromine.

R¹, R², R³ and R⁴ can also be substituted mono- or diphenylsulfamoyl andmono- or diphenylcarbamoyl whose phenyl(s) carries (carry) preferablytwo, three or, in particular, one substituent(s) from the groupconsisting of nitro, cyano, C₁ -C₄ -alkoxycarbonyl and carboxyl.

The quinacridones of the formula I preferably carry substituents R¹, R²,R³ and R⁴ from the group consisting of C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy,chlorine, sulfamoyl, mono- and di-(C₁ -C₄)-alkylsulfamoyl and mono- anddiphenylsulfamoyl.

Particular preference is given to quinacridones of the formula I inwhich R² and R⁴ are hydrogen.

Preference is also given to quinacridones of the formula I in which R³=R¹ and R⁴ =R².

Preference is given to quinacridones of the formula I in which n and mare each 1.

The preparation of quinacridonesulfonic acids is known and is describedin U.S. Pat. No. 3,386,843. Consequently, the alkali metal salts arereadily obtainable by reacting the acids with the corresponding alkalimetal hydroxides. Likewise starting from the acids, this time byreaction with primary, secondary or tertiary amines or quaternaryammonium salts, the ammonium salts can be obtained. This reaction can becarried out in water and in polar organic solvents such as methanol,ethanol, acetone or dimethylformamide, for example.

The novel ammonium salts of the general formula I, where M.sup.⊕ isNH₄.sup.⊕, are obtained, for example, by reacting thequinacridone-sulfonic acids with a concentrated aqueous ammoniasolution, advantageously at room temperature.

It has been found that the water-soluble quinacridones I are suitablefor dyeing and printing natural and synthetic fiber material such ascotton, wool or nylon. They are particularly preferred for use in thepulp dyeing of paper and in the inkjet printing process.

The pulp dyeing of paper is preferably employed with sized or unsizedpaper.

In the inkjet printing process the inks used are usually aqueous inkswhich are sprayed in small droplets directly onto the substrate. Adistinction is made here between a continuous process, in which the inkis pressed uniformly through a nozzle and is guided onto the substrateby means of an electrical field depending on the pattern to be printed,and an interrupted inkjet, or drop-on-demand process, where the ink isejected only where a colored dot is to appear. In the latter process,pressure is exerted on the ink system by way of either a piezoelectriccrystal or a heated hollow needle (bubblejet or thermal jet process) andso one drop of ink is expelled. Techniques of this kind are described,for example, in Text. Chem. Color, Volume 19 (8), 1987, pages 23 to 29and Volume 21 (6), 1989, pages 27 to 32.

The dyeings or prints obtained in this process feature particularly goodwet fastness and abrasion fastness. They are resistant not only to waterbut also to milk, soapy water, sodium chloride solution, fruit juices,sweetened mineral waters and alcoholic drinks. The inks and recordingliquids comprising these dyes have outstanding stability on storage andproduce printed images of high definition, brightness and fastness. Evenduring storage of the inks and recording liquids there is no deposition,which can lead to blockage of nozzles or to printed images lacking indefinition.

The present invention also provides mixtures, for example recordingliquids, comprising the quinacridones of the formula I. These recordingliquids may include either only dissolved dyes or else pigments as well,for example C.I. Pigment Violet 19 or C.I. Pigment Red 122. Recordingliquids are prepared by methods known per se. The recording liquidsgenerally contain a total of from 0.5 to 15% by weight of one or moredyes of the formula I, from 0 to 99% by weight of water and from 0.5 to99.5% by weight of a water-soluble organic solvent, the sum of all thecomponents being 100. Examples of suitable solvents are mono- andpolyhydric alcohols, their ethers and esters.

Examples of suitable solvents are ethanol, propanol, isopropanol,butanol, isobutanol and tert-butanol; dihydric and trihydric alcohols,especially those having from 2 to 6 carbons, examples being ethyleneglycol, propylene glycol, 1,3-propanediol, 1,4-butanediol,1,5-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, glycerol, diethyleneglycol, dipropylene glycol; polyalkylene glycols, for exampletriethylene glycol, polyethylene glycol, tripropylene glycol,polypropylene glycol; lower alkyl ethers of polyhydric alcohols, forexample ethylglycol monomethyl or monoethyl or monopropyl or monobutylether, diethylene glycol monomethyl or monoethyl ether, triethyleneglycol monomethyl or monoethyl ether; ketones and keto alcohols,especially those having from 3 to 7 carbon atoms, such as acetone,methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, methylpentyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol; ethers,for example dibutyl ether, tetrahydrofuran, dioxane; esters, for exampleethyl formate, methyl formate, methyl acetate, ethyl acetate, propylacetate, butyl acetate, phenyl acetate, ethylene glycol monoethyl etheracetate, 2-hydroxyethyl acetate; amides, for example dimethylformamide,dimethylacetamide, N-methylpyrrolidone; and also urea, tetramethylureaand thiodiglycol.

The recording liquids may also comprise customary additives, examplesbeing preservatives, such as phenol derivatives, cationic, anionic ornonionic surface-active substances (wetting agents), and also viscosityregulators, for example polyvinyl alcohol, cellulose derivatives, sugarderivatives or water-soluble natural or synthetic resins as film formersand/or binders for increasing the adhesive strength and abrasionresistance.

Amines, such as ethanolamine, diethanolamine, triethanolamine,N,N-dimethylethanolamine and diisopropylamine, for example, serveprimarily to raise the pH of the recording liquid. They are generallypresent in proportions of from 0 to 10% by weight, preferably from 0.5to 5% by weight, in the recording liquid.

In the case of recording liquids for the inkjet printing process, anddepending on the particular embodiment of this process, for examplecontinuous jet, intermittent jet, impulse jet or compound jet processes,it may be appropriate to add further additives, for example forbuffering the pH or for adjusting the electrical conductivity, specificheat or coefficient of thermal expansion.

The recording liquids can be prepared simply by mixing the components,for example by dissolving one or more dyes of the formula I in waterand/or solvent or else by diluting an aqueous solution obtained in thepreparation of the dye of formula I, possibly after appropriatepreparation, to the desired extent and then adding further components,such as water, solvents, additives, etc.

The recording liquids comprising one or more dyes of the formula I areoutstandingly suited to use in printing, copying, marking, writing,drawing, stamping or recording processes, including in particular theinkjet printing process.

The application also embraces novel quinacridones of the formula II##STR3## where R¹, R², R³, R⁴, m and n are as defined in claim 1 and thesum of n+m is at least 1.

R¹, R², R³ and R⁴ are preferably as already defined for thequinacridones of the formula I. Similarly, the same preferences apply tothe quinacridones II.

The novel quinacridones are suitable for the dyeing and printing ofnatural and synthetic fiber material. The present invention likewiseembraces mixtures comprising quinacridones of the formula II, especiallyrecording liquids.

Preparing the dyes

EXAMPLE 1

14.6 g of the diphenylaminoterephthalic acid derivative described inU.S. Pat. No. 3,386,843 ##STR4## were introduced with stirring into 292g of polyphosphoric acid and then the mixture was heated at 160° C. for6 hours. Subsequently, it was cooled and the violet solution wasprecipitated in 1000 ml of ice-cold methanol. The resulting precipitatewas filtered off with suction, washed with methanol and dried. Theresulting 2,9-quinacridonedisulfonic acid was stirred at roomtemperature for 2 hours with 50 ml of concentrated aqueous ammoniasolution. The bisammonium salt was then precipitated by adding acetoneand was isolated. For additional purification, it was again dissolved ina little water and precipitated with acetone. Drying gave 8.1 g of thecompound of the formula ##STR5## Analysis: C₂₀ H₂₆ O₁₂ N₄ S₂, MW 578.6

    ______________________________________                                        C             H      O          N    S                                        ______________________________________                                        Calc.   41.52     4.53   33.18    9.68 11.08                                  Found   41.6      4.2    32.5     10.0 10.8                                   ______________________________________                                    

UV(H₂ O): λ: 532 nm (ε: 5800), 502 nm (ε: 6430)

The alkali metal salts and other ammonium salts were preparedanalogously by neutralizing the quinacridonedisulfonic acid with alkalimetal hydroxides or amines. The reaction can be carried out in water orin organic solvents such as methanol, ethanol, acetone or DMF, forexample.

EXAMPLE 2

The disodium salt of 2,9-quinacridonedisulfonic acid, prepared inaccordance with U.S. Pat. No. 3,386,843, was purified by dissolving ittwice in the minimum amount of water and then precipitating it withethanol. ##STR6## UV(H₂ O): λ: 528 nm (ε: 4480), 498 nm (ε: 4980)

USE EXAMPLE

A 3% strength by weight solution comprising 0.3 g of the dye prepared inExample 1 and 9.7 g of a 10% strength by weight aqueous solution ofN-methylpyrrolidone was prepared by stirring the mixture at roomtemperature for 2 hours.

The resulting ink was then used for printing with an inkjet printer inaccordance with the bubble-jet technique.

The prints obtained had good applications-related properties.

We claim:
 1. A method of dyeing and printing a natural or syntheticfiber material, comprising:contacting the fiber material with awater-soluble quinacridone represented by formula I: ##STR7## whereinM.sup.⊕ is a lithium, sodium, potassium or ammonium cation, R¹, R², R³and R⁴ are, independently, hydrogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy,carboxyl, C₁ -C₄ -alkoxycarbonyl, sulfamoyl, mono- or di-(C₁-C₄)-alkylsulfamoyl, carbamoyl, mono- or di-(C₁ -C₄)-alkylcarbamoyl,unsubstituted or substituted mono- or diphenylsulfamoyl, unsubstitutedor substituted mono- or diphenylcarbamoyl, halogen, nitro or cyano, n is0, 1 or 2, m is 0, 1 or 2, and the sum n+m is at least
 1. 2. The methodof claim 1, wherein M.sup.⊕ is an unsubstituted ammonium cation.
 3. Themethod of claim 1, which is an inkjet printing process.
 4. The method ofclaim 1, comprising the pulp dyeing of paper.
 5. A mixture,comprising:0-99% by weight of water, 0.5-99.5% by weight of awater-soluble organic solvent, and 0.5-15% by weight of a quinacridonerepresented by formula I: ##STR8## wherein M.sup.⊕ is a lithium, sodium,potassium or an unsubstituted ammonium cation, R¹, R², R³ and R⁴ are,independently, hydrogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, carboxyl, C₁ -C₄-alkoxycarbonyl, sulfamoyl, mono- or di-(C₁ -C₄)-alkylsulfamoyl,carbamoyl, mono- or di-(C₁ -C₄)-alkylcarbamoyl, unsubstituted orsubstituted mono- or diphenylsulfamoyl, unsubstituted or substitutedmono- or diphenylcarbamoyl, halogen, nitro or cyano, n is 0, 1 or 2, mis 0, 1 or 2, and the sum n+m is at least
 1. 6. A quinacridonerepresented by formula II: ##STR9## wherein R¹, R², R³ and R⁴ are,independently, hydrogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, carboxyl, C₁ -C₄-alkoxycarbonyl, sulfamoyl, mono- or di-(C₁ -C₄)-alkylsulfamoyl,carbamoyl, mono- or di-(C₁ -C₄)-alkylcarbamoyl, unsubstituted orsubstituted mono- or diphenylsulfamoyl, unsubstituted or substitutedmono- or diphenylcarbamoyl, halogen, nitro or cyano,n is 0, 1 or 2, m is0, 1 or 2, and the sum n+m is at least
 1. 7. A mixture comprising one ormore quinacridones represented by formula II as claimed in claim
 6. 8. Amethod of ink jet printing a natural or synthetic fiber material,comprising:contacting the fiber material with a water-solublequinacridone represented by formula I: ##STR10## wherein M.sup.⊕ is alithium, sodium, potassium or ammonium cation, R¹, R², R³ and R⁴ are,independently, hydrogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, carboxyl, C₁ -C₄-alkoxycarbonyl, sulfamoyl, mono- or di-(C₁ -C₄)-alkylsulfamoyl,carbamoyl, mono- or di-(C₁ -C₄)-alkylcarbamoyl, unsubstituted orsubstituted mono- or diphenylsulfamoyl, unsubstituted or substitutedmono- or diphenylcarbamoyl, halogen, nitro or cyano, n is 0, 1 or 2, mis 0, 1 or 2, and the sum n+m is at least
 1. 9. A method of pulp dyeingpaper, comprising:contacting the fiber material with a water-solublequinacridone represented by formula I: ##STR11## wherein M.sup.⊕ is alithium, sodium, potassium or ammonium cation, R¹, R², R³ and R⁴ are,independently, hydrogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, carboxyl, C₁ -C₄-alkoxycarbonyl, sulfamoyl, mono- or di-(C₁ -C₄)-alkylsulfamoyl,carbamoyl, mono- or di-(C₁ -C₄)-alkylcarbamoyl, unsubstituted orsubstituted mono- or diphenylsulfamoyl, unsubstituted or substitutedmono- or diphenylcarbamoyl, halogen, nitro or cyano, n is 0, 1 or 2, mis 0, 1 or 2, and the sum n+m is at least
 1. 10. A quinacridonerepresented by formula I: ##STR12## wherein R¹, R², R³ and R⁴ are,independently, hydrogen, C₁ -C₈ -alkyl, C₁ -C₈ -alkoxy, carboxyl, C₁ -C₄-alkoxycarbonyl, sulfamoyl, mono- or di-(C₁ -C₄)-alkylsulfamoyl,carbamoyl, mono- or di-(C₁ -C₄)-alkylcarbamoyl, unsubstituted orsubstituted mono- or diphenylsulfamoyl, unsubstituted or substitutedmono- or diphenylcarbamoyl, halogen, nitro or cyano,M⁺ is lithium orpotassium, n is 0, 1 or 2, m is 0, 1 or 2, and the sum n+m is at least1.